Singling Out Dynamic and Nondynamic Correlation

Abstract

The correlation part of the pair density is separated into two components, one of them being predominant at short electronic ranges and the other at long ranges. The analysis of the intracular part of these components permits to classify molecular systems according to the prevailing correlation: dynamic or nondynamic. The study of the long-range asymptotics reveals the key component of the pair density that is responsible for the description of London dispersion forces and a universal decay with the interelectronic distance. The natural range-separation, the identification of the dispersion forces, and the kind of predominant correlation type that arise from this analysis are expected to be important assets in the development of new electronic structure methods in wave function, density, and reduced density-matrix functional theories.

This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in J. Phys. Chem. Lett., copyright American Chemical Society after peer review. To access the final edited and published work see http://doi.org/10.1021/acs.jpclett.9b01376

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• 1-matrix functional for long-range interaction energy of two hydrogen atoms
• Variations of the Hartree-Fock fractional-spin error for one electron
• $\Delta$NO and the complexities of electron correlation in simple hydrogen clusters
• Partition of Optical Properties Into Orbital Contributions
• Range separation of the Coulomb hole
• Measuring correlated electron motion in atoms with the momentum-balance density
• Relativistic effects on electronic pair densities: a perspective from the radial intracule and extracule probability densities
• The Wigner localization of interacting electrons in a one-dimensional harmonic potential
• Time-Reversal Symmetry in RDMFT and pCCD with Complex-Valued Orbitals
• Capturing electron correlation at mean-field cost: Assessment of i-DMFT and the underlying correlation conjecture